US20120328877A1 - Cellulose nanofibers, method for producing same, composite resin composition and molded body - Google Patents

Cellulose nanofibers, method for producing same, composite resin composition and molded body Download PDF

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US20120328877A1
US20120328877A1 US13/603,806 US201213603806A US2012328877A1 US 20120328877 A1 US20120328877 A1 US 20120328877A1 US 201213603806 A US201213603806 A US 201213603806A US 2012328877 A1 US2012328877 A1 US 2012328877A1
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cellulose nanofibers
resin composition
cellulose
composite resin
molded body
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Kohei Shiramizu
Naohito Shiga
Takashi Magara
Kohei Oguni
Lianzhen Lin
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Olympus Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • the present invention relates to cellulose nanofibers, a methd for producing the same, a composite resin composition, and a molded body.
  • Cellulose nanofibers have been used as a reinforcing material for polymeric composite materials in the related art.
  • the cellulose nanofibers are generally obtained by mechanically shearing cellulose fibers such as pulp.
  • Japanese Patent Application, First Publication No. 2000-17592 discloses fibrillar cellulose that is obtained by treating an aqueous cellulose pulp suspension with a high-pressure homogenizer.
  • Japanese Patent Application, First Publication No. H09-291102 discloses acetyl cellulose ultrafine fibers that are obtained by acetylating ultrafine cellulose fibers produced from bacteria.
  • the ultrafine cellulose fibers produced from bacteria have a mass-average polymerization degree of 1700 or higher. Accordingly, the ultrafine cellulose fibers produced from bacteria are excellent in terms of Young's modulus and tensile strength.
  • the invention employs the following means.
  • the cellulose nanofibers of the present invention have an average polymerization degree of 600 to 30000, an aspect ratio of 20 to 10000, an average diameter of 1 nm to 800 nm, and an I ⁇ -type crystal peak in an X-ray diffraction pattern.
  • hydroxyl groups are preferably chemically modified with a modification group.
  • a saturated absorptivity in an organic solvent having an SP value of 8 to 13 is preferably 300% by mass to 5000% by mass.
  • the organic solvent is preferably a water-insoluble solvent.
  • the hydroxyl groups are preferably esterified or etherified by the modification group.
  • 0.01% to 50% of the total hydroxyl groups are preferably chemically modified.
  • the composite resin composition of the present invention contains the cellulose nanofibers in a resin.
  • An average light transmittance at 400 nm to 700 nm of the composite resin composition of the present invention is preferably 60% or more.
  • the molded body of the present invention is obtained by molding the composite resin composition.
  • a cellulose raw material is defibrated and chemically modified in a solution containing an ionic liquid.
  • FIG. 1 is a view illustrating results of X-ray diffraction analysis of the cellulose nanofibers of the present invention.
  • the average polymerization degree of the cellulose nanofibers of the present invention is 600 to 30000.
  • the average polymerization degree is preferably 600 to 5000, and more preferably 800 to 5000. If the average polymerization degree is 600 or higher, a sufficient reinforcing effect can be obtained.
  • the cellulose nanofibers in the related art are obtained by performing mechanical shearing such as homogenizing treatment on a raw material of cellulose fibers. Consequently, the cellulose nanofibers in the related art have a low polymerization degree, and a sufficient reinforcing effect cannot be obtained. Moreover, since the mechanical shearing seriously damages the raw material of cellulose fibers, the strength and the aspect ratio of the obtained cellulose nanofibers are low. According to the method for producing the cellulose nanofibers of the present invention that is described later, the raw material of cellulose fibers is not damaged. Accordingly, it is possible to easily obtain cellulose nanofibers having a polymerization degree of 600 or higher.
  • the aspect ratio of the cellulose nanofibers of the present invention is 20 to 10000 and more preferably 20 to 2000.
  • the “aspect ratio” refers to a ratio (average fiber length/average diameter) between an average fiber length and an average diameter of the cellulose nanofibers.
  • the average diameter of the cellulose nanofibers of the present invention is 1 nm to 800 nm, preferably 1 nm to 300 nm, and more preferably 1 nm to 100 nm. If cellulose nanofibers having an average diameter of 1 nm or more are produced, the production cost can be kept low. If cellulose nanofibers having an average diameter of 800 nm or less are produced, decrease in the aspect ratio can be inhibited. As a result, the cellulose nanofibers of the present invention can obtain a sufficient reinforcing effect with a low cost.
  • the cellulose nanofibers of the present invention have an I ⁇ -type crystal peak in an X-ray diffraction pattern.
  • a cellulose type I is composite crystals of I ⁇ -type crystals and I ⁇ -type crystals.
  • Cellulose derived from higher plants such as cotton includes more I ⁇ -type crystals than I ⁇ -type crystals.
  • Bacterial cellulose includes more I ⁇ -type crystals than I ⁇ -type crystals. Since the cellulose nanofibers of the present invention obtained using wood and the like, they mainly include the I ⁇ -type crystals.
  • the cellulose nanofibers of the present invention show a pattern unique to the I ⁇ -type crystals in an X-ray diffraction pattern as shown in FIG. 1 .
  • the cellulose nanofibers of the present invention mainly include the I ⁇ -type crystals, the reinforcing effect thereof is superior to that of bacterial cellulose including lots of I ⁇ -type crystals.
  • the cellulose nanofibers of the present invention may be chemically modified so as to enhance its functionality.
  • the number of hydrogen bonds formed between the cellulose nanofibers is reduced, whereby strong adhesion between the cellulose nanofibers can be prevented. Consequently, the cellulose nanofibers are easily dispersed in a polymer material, whereby excellent interfacial bonds can be formed between the cellulose nanofibers and the polymer material.
  • the cellulose nanofibers of the present invention Due to the chemical modification, the cellulose nanofibers of the present invention have thermal resistance. Accordingly, if the chemically modified cellulose nanofibers of the present invention are mixed with other material, it is possible to impart thermal resistance to other material.
  • the proportion of hydroxyl groups chemically modified by a modification group with respect to total hydroxyl groups in the cellulose nanofibers is preferably 0.01% to 50%, and more preferably 10% to 20%.
  • the chemical modification simply needs to cause a reaction with a hydroxyl group.
  • Etherification or esterification of the cellulose nanofibers is preferable since the chemical modification can be performed simply and efficiently.
  • alkyl halides such as methyl chloride and ethyl chloride
  • dialkyl carbonate such as dimethyl carbonate and diethyl carbonate
  • dialkyl sulfate such as dimethyl sulfate and diethyl sulfate
  • alkylene oxides such as ethylene oxide and propylene oxide; and the like
  • the etherification is not limited to alkyl etherification caused by the above etherification agents, and etherification caused by benzyl bromide, silyl etherification, and the like are also preferable.
  • silyl etherification agents include alkoxysilanes such as n-butoxytrimethylsilane, tert-butoxytrimethylsilane, sec-butoxytrimethylsilane, isobutoxytrimethylsilane, ethoxytriethylsilane, octyldimethylethoxysilane, and cyclohexyloxytrimethylsilane; alkoxysiloxanes such as butoxypolydimethylsiloxane; and silazanes such as hexamethyldisilazane, tetramethyldisilazane, and diphenyltetramethyldisilazane.
  • alkoxysilanes such as n-butoxytrimethylsilane, tert-butoxytrimethylsilane, sec-butoxytrimethylsilane, isobutoxytrimethylsilane, ethoxytriethylsilane, octyldimethylethoxys
  • silyl halides such as trimethylsilyl chloride and diphenylbutyl chloride
  • silyl trifluoromethane sulfonates such as t-butyldimethylsilyl trifluoromethane sulfonate can also be used.
  • esterification agents include a carboxylic acid that may have a hetero atom, a carboxylic anhydride, and a carboxylic halide.
  • esterification agents acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, and a derivative of these are preferable, and acetic acid, acetic anhydride, and butyric anhydride are more preferable.
  • alkyl etherification alkyl silylation, and alkyl esterification are preferable since dispersibility in a resin is improved by these reactions.
  • the saturated absorptivity of the cellulose nanofibers of the present invention chemically modified described above is preferably 300% by mass to 5000% by mass in an organic solvent having a solubility parameter (hereinbelow, referred to as an SP value) of 8 to 13.
  • the cellulose nanofibers dispersed in the organic solvent having the above SP value have high affinity with a lipophilic resin and have a high reinforcing effect.
  • organic solvents having an SP value of 8 to 13 include acetic acid, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, methyl propyl ketone, methyl isopropyl ketone, xylene, toluene, benzene, ethyl benzene, dibutyl phthalate, acetone, isopropanol, acetonitrile, dimethyl formamide, ethanol, tetrahydrofuran, methyl ethyl ketone, cyclohexane, carbon tetrachloride, chloroform, methylene chloride, carbon disulfide, pyridine, n-hexanol, cyclohexanol, n-butanol, nitromethane, and the like.
  • water-insoluble solvents solvents that do not mix with water at 25° C. water at any ratio
  • water-insoluble solvents solvents that do not mix with water at 25° C. water at any ratio
  • xylene, toluene, benzene, ethylbenzene, dichloromethane, cyclohexane, carbon tetrachloride, methylene chloride, ethyl acetate, carbon disulfide, cyclohexanol, and nitromethane are more preferable.
  • the cellulose nanofibers of the present invention that are chemically modified as described above can be dispersed even in a water-insoluble solvent. Therefore, while cellulose nanofibers in the related art are not easily dispersed in a lipophilic resin, the cellulose nanofibers of the present invention that are chemically modified as described above can be easily dispersed in a lipophilic resin.
  • the lipophilic resin resins that dissolve poorly in water and are widely used as an industrial material required to have water resistance are preferable.
  • the lipophilic resin may be either a thermoplastic resin or a thermosetting resin.
  • the lipophilic resin particularly include a plant-derived resin, a resin formed of carbon dioxide as a raw material, an ABS resin, alkylene resins such as polyethylene and polypropylene, a styrene resin, a vinyl resin, an acrylic resin, an amide resin, an acetal resin, a carbonate resin, a urethane resin, an epoxy resin, an imide resin, a urea resin, a silicone resin, a phenol resin, a melamine resin, an ester resin, an acrylic resin, an amide resin, a fluoro resin, a styrol resin, an engineering plastic, and the like.
  • polyamide, polybutylene terephthalate, polycarbonate, polyacetal, modified polyphenylene oxide, modified polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyether sulfone, polysulfone, polyamide imide, polyether imide, polyimide, polyarylate, polyallyl ether nitrile, and the like are preferable.
  • the above resins two or more kinds of resins may be used as a mixture.
  • polycarbonate is particularly preferable due to its strong impact strength.
  • polycarbonate generally used polycarbonate can be used.
  • aromatic polycarbonate produced from a reaction between an aromatic dihydroxy compound and a carbonate precursor is preferable.
  • aromatic dihydroxy compound examples include 2,2-bis(4-hydroxyphenyl)propane (“bisphenol A”), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ketone, and the like.
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • bis(4-hydroxyphenyl)methane 1,1-bis(4-hydroxyphenyl)ethane
  • 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane 4,4′-dihydroxydipheny
  • polycarbonate precursor examples include carbonyl halides, carbonyl esters, haloformates, and the like.
  • the polycarbonate precursor is specifically phosgene, dihaloformate of, a divalent phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate, and the like.
  • the polycarbonate may be polycarbonates excluding aromatic polycarbonate.
  • examples of the polycarbonates excluding aromatic polycarbonate include alicyclic polycarbonate, aliphatic polycarbonate, and the like.
  • the polycarbonate resin may be linear or branched.
  • the polycarbonate resin may also be a copolymer of a polymer, which is obtained by polymerizing the aromatic dihydroxy compound and the carbonate precursor, with another polymer.
  • the polycarbonate resin can be produced by a method known in the related art.
  • methods known in the related art include various methods such as interfacial polymerization, melt transesterification, a pyridine method, and the like.
  • the type of the resin usable in the composite resin composition of the present invention includes a hydrophilic resin, in addition to the lipophilic resin described above.
  • a hydrophilic resin for example, unmodified cellulose nanofibers or cellulose nanofibers chemically modified with hydrophilic functional groups such as a sulfonic acid group, a carboxylic acid group, or a salt of these disperse excellently in a hydrophilic resin and can be suitably used.
  • the hydrophilic resin include polyvinyl alcohol, resins having undergone hydrophilication treatment, and the like. Among these, polyvinyl alcohol is particularly preferable since this resin is inexpensive and the cellulose nanofibers disperse excellently in this resin.
  • Additives such as a filler, a flame retarding aid, a flame retardant, an antioxidant, a release agent, a colorant, and a dispersant may be further added to the composite resin composition of the present invention.
  • carbon fibers As the filler, carbon fibers, glass fibers, clay, titanium oxide, silica, talc, calcium carbonate, potassium titanate, mica, montmorillonite, barium sulfate, a balloon filler, a beads filler, carbon nanotubes, and the like are usable.
  • a halogen-based flame retardant As the flame retardant, a halogen-based flame retardant, a nitrogen-based flame retardant, metal hydroxide, phosphorus-based flame retardant, an organic alkali metal salt, an organic alkaline earth metal salt, a silicone-based flame retardant, expandable graphite, and the like are usable.
  • polyfluoroolefin As the flame retarding aid, polyfluoroolefin, antimony oxide, and the like are usable.
  • antioxidant a phosphorus-based antioxidant, a phenol-based antioxidant, and the like are usable.
  • a higher alcohol, carboxylic acid ester, polyolefin wax, polyalkylene glycol, and the like are usable.
  • any colorants such as carbon black and phthalocyanine blue are usable.
  • surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants and polymeric dispersants are usable, and the surfactant and the polymeric dispersant can be used concurrently, as long as the dispersant enables the cellulose nanofibers to be dispersed in the resin.
  • the composite resin composition of the present invention that contains the cellulose nanofibers has excellent transparency.
  • an average light transmittance at 400 nm to 700 nm is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. When the average light transmittance is 60% or more, transparency is maintained, so the composite resin composition can be suitably used for usage requiring transparency.
  • the composite resin composition containing the chemically modified cellulose nanofibers can realize the decrease in a water absorbency and the improvement of thermal resistance without decreasing the light transmittance.
  • the molded body of the present invention is obtained by molding the composite resin composition. Since the molded body of the present invention also contains the cellulose nanofibers, the molded body has excellent strength and thermal resistance. Though not particularly limited, the molded body is used for medical instruments, audio equipment, and the like. Particularly, the molded body is suitably used as a molded body for a camera and a mirror frame that require strength.
  • a cellulose raw material is defibrated and chemically modified in a solution containing an ionic liquid, whereby the cellulose nanofibers are produced.
  • the cellulose raw material is not particularly limited.
  • the cellulose raw material include raw materials of natural cellulose such as cotton and hemp; pulp obtained by chemically treating wood, such as kraft pulp and sulfide pulp; semi-chemical pulp; used paper or recycled pulp thereof; and the like.
  • pulp obtained by chemically treating wood is preferable in view of the cost, quality, and influence on the environment.
  • the shape of the cellulose raw material is not particularly limited. However, in view of easiness of treatment and accelerating solvent permeation, the cellulose raw material is preferably used after being appropriately pulverized.
  • the solution (hereinbelow, referred to as a treatment solution) containing the ionic liquid is a solvent that contains an ionic liquid represented by the following chemical formula and an organic solvent.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms
  • R 2 represents an alkyl group having 1 to 4 carbon atoms or an allyl group
  • X ⁇ represents halogen, pseudo-halogen, carboxylate having 1 to 4 carbon atoms, or thiocynate.
  • Examples of the ionic liquid include 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, and 1-propyl-3-methylimidazolium bromide.
  • the type of organic solvent to be added may be appropriately selected in consideration of compatibility with the ionic liquid, affinity with cellulose or a chitin material, solubility of a mixed solvent, viscosity, and the like. Particularly, it is preferable to use any one or more organic solvents from among N,N-dimethylacetamide, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, dimethylsulfoxide, acetonitrile, methanol, and ethanol. If these organic solvents are used concurrently, permeation of the ionic liquid into fine cellulose fibers is promoted, whereby destruction of the crystal structure of the fine fibers caused by the ionic liquid can be prevented.
  • the amount of the ionic liquid contained in the treatment solution may be appropriately adjusted since the amount depends on the type of the cellulose raw material, the ionic liquid, and the organic solvent.
  • the amount of the ionic liquid contained in the treatment solution is preferably 20% by mass or more in view of swelling and solubility, and when an organic solvent having high solubility is used, the amount is more preferably 30% by mass or more.
  • the amount is particularly preferably 50% by mass or more.
  • the amount of the cellulose raw material added preferably ranges from 0.5% by mass to 30% by mass based on the treatment solution. In view of economic efficiency, the amount of the cellulose raw material added is 0.5% by mass or more, and more preferably 1% by mass or more, based on the treatment solution. On the other hand, in view of uniformity of the defibration degree, the amount of the cellulose raw material added is preferably 30% or less, and more preferably 20%, based on the treatment solution.
  • an appropriate temperature at which the cellulose raw material swells, and a bound substance between fine fibers softens and dissolves may be selected.
  • the treatment temperature is preferably 20° C. to 120° C. in general.
  • the treatment temperature is 20° C. or higher, the defibration effect is not diminished, in view of the treatment rate and the viscosity of the treatment solution. If the treatment temperature is 120° C. or lower, the bound substance between the fine fibers does not excessively soften and dissolve. Accordingly, when the treatment temperature is 20° C. to 120° C., a yield of the cellulose nanofibers can be maintained.
  • the method for producing the cellulose nanofibers of the present invention after the defibration treatment performed in the treatment solution, chemical modification is performed.
  • the chemical modification the etherification, esterification, and silylation described above are preferable.
  • cellulose nanofibers of the present invention fibers are not damaged. Accordingly, it is possible to obtain cellulose nanofibers having a polymerization degree of 600 or higher that do not exist in the related art.
  • the cellulose nanofibers obtained in Example 1 were acetylated using acetic anhydride (esterification agent), thereby obtaining acetylated cellulose nanofibers.
  • the modification rate of the cellulose nanofibers obtained at this time was 10%.
  • polycarbonate which had already been dissolved in dichloromethane was mixed with acetylated cellulose nanofibers in the dichloromethane, followed by drying. Thereby, a polycarbonate composite resin composition containing cellulose nanofibers was obtained.
  • a polycarbonate composite resin composition containing cellulose nanofibers was obtained by the same process as in Example 2, except that the amount of the acetic anhydride was increased by twice that in Example 2.
  • the modification rate of the cellulose nanofibers obtained at this time was 18%.
  • a polycarbonate composite resin composition containing cellulose nanofibers was obtained by the same process as in Example 2, except that hexamethyldisilazane (silyl etherification agent) was added instead of acetic anhydride.
  • the modification rate of the cellulose nanofibers obtained at this time was 15%.
  • a polycarbonate composite resin composition containing cellulose nanofibers was obtained by the same process as in Example 2, except that bacterial cellulose obtained by drying NATA de COCO (manufactured by Fujicco Co., Ltd., average polymerization degree: 3000 or higher, average aspect ratio: 1000 or more, average diameter: 70 nm) was used.
  • NATA de COCO manufactured by Fujicco Co., Ltd., average polymerization degree: 3000 or higher, average aspect ratio: 1000 or more, average diameter: 70 nm
  • a polycarbonate composite resin composition containing cellulose nanofibers was obtained in the same process as in Example 2, except that fine crystalline cellulose (manufactured by MERCK LTD., average polymerization degree: 250, average aspect ratio: 10, diameter: crystals having a diameter of 1 ⁇ m to 10 ⁇ m are mixed) was used.
  • the average polymerization degree was measured by the copper ethylenediamine method disclosed in “The Society of Polymer Science, Japan, “Polymer material testing method 2”, p. 267, KYORITSU SHUPPAN CO., LTD. (1965)”.
  • the number average fiber diameter and the number average length of the cellulose nanofibers were evaluated by SEM analysis.
  • a cellulose nanofiber dispersion was cast on a wafer so as to be observed by SEM, and for each of the obtained images, the values of fiber diameter and length were read out with respect to 20 or more strands of fibers. This operation was performed on at least 3 sheets of images of non-overlapping regions, thereby obtaining information on the diameter and length of a minimum of 30 strands of fiber.
  • the number average fiber diameter and the number average length could be calculated. From a ratio between the number average length and the number average fiber diameter, the aspect ratio was calculated. When the aspect ratio was 20 to 10000, this was determined to be O, and when the aspect ratio was not 20 to 10000, this was determined to be X.
  • the crystal structure of the cellulose nanofibers was analyzed using a powder X-ray diffraction instrument Rigaku Ultima IV. When the X-ray diffraction pattern showed the pattern unique to the I ⁇ -type crystals, this was determined to be O. Cases other than this were determined to be ⁇ . In addition, when the crystal structure of the cellulose nanofibers was an I ⁇ -type crystal structure in examples and comparative examples, this was indicated as O, and when the crystal structure was not the I ⁇ -type crystal structure, this was indicated as X.
  • the modification rate of hydroxyl groups was calculated from an elemental ratio between carbon, hydrogen, and oxygen that was obtained by elemental analysis.
  • cellulose nanofibers of a weight (W 1 ) were dispersed in dichloromethane (SP value 9.7), thereby preparing a dispersion of 2 wt %. Subsequently, this dispersion was put in a centrifuge flask, followed by centrifugation for 30 minutes at 4500 G. Thereafter, a transparent solvent layer in the upper portion of the centrifuged dispersion was removed, and then a weight (W 2 ) of a gel layer in the lower portion was measured. From the result, the saturated absorptivity was calculated by the following formula.
  • Example 3 the evaluation was performed using two solvents including ethyl acetate (SP value 9.1) and dichloromethane (SP value 9.7). At this time, the amount of ethyl acetate was 1200% by mass, and the amount of dichloromethane was 1500% by mass.
  • SP value 9.1 ethyl acetate
  • SPD value 9.7 dichloromethane
  • a resin film having a thickness of 20 ⁇ m and containing 2 wt % of the cellulose nanofibers was prepared, and a transmittance at 600 nm was measured using UV 3600 manufactured by Shimadzu Corporation. When the cellulose nanofibers were not mixed with a resin in visual observation, this was determined to be X.
  • Example 2 Example 3
  • Example 4 Example 1
  • Example 2 Polymerization 800 800 800 600 3000 250 degree Aspect ratio 106 100 95 103 1000 10
  • Average 100 100 100 100 70 1000 diameter (nm) Crystal type ⁇ ⁇ ⁇ ⁇ X ⁇ Modification 0 10 18 15 0 0 rate (%)
  • the molded body of the present invention was excellent in terms of the average light transmittance. Moreover, Examples 2 to 4 in which hydroxyl groups of the cellulose nanofibers of the present invention were chemically modified were superior in the saturated absorptivity, compared to Comparative Examples 1 and 2.
  • the obtained composite resin compositions containing cellulose nanofibers were thermally melted and molded, and the molded state was judged by visual observation. When the moldability was excellent, this was determined to be O, and when the moldability was poor, this was determined to be X.
  • a linear hest expansion coefficient between 100° C. and 180° C. was measured using Thermo plus TMA 8310 manufactured by Rigaku Corporation in an air atmosphere heated at a heating rate of 5° C./min.
  • the size of a test sample was set to 20 mm (length) x5 mm (width).
  • a first-run was carried out at a temperature ranging from room temperature to Tg, and then the temperature was cooled to room temperature to carry out a second-run. From the results, a linear heat expansion coefficient was calculated by the following formula.
  • Linear heat expansion coefficient (length at a point in time of 180° C. ⁇ length at a point in time of 40° C.)/length at a point in time of 40° C. ⁇ 100 ⁇ 100
  • Example 2 Example 3
  • Example 4 Example 1
  • Example 2 Moldability ⁇ ⁇ ⁇ ⁇ X ⁇ Linear heat ⁇ ⁇ ⁇ ⁇ ⁇ X expansion coefficient
  • the molded bodies of the present invention obtained in examples showed moldability and linear heat expansion coefficients superior to those of comparative examples.
  • cellulose nanofibers having an excellent reinforcing effect
  • a method for producing the cellulose nanofibers a composite resin composition containing the cellulose nanofibers, and a molded body obtained by molding the composite resin composition.

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Abstract

The present invention is cellulose nanofibers having an average polymerization degree of 600 to 30000, an aspect ratio of 20 to 10000, an average diameter of 1 nm to 800 nm, and an Iβ-type crystal peak in an X-ray diffraction pattern.

Description

  • The present application is a continucation application based on International Patent Application No. PCT/JP2011/054,325, filed Feb. 25, 2011. In the International Patent Application, priority is claimed on Japanese Patent Application No. 2010-049565, filed Mar. 5, 2010, the content of which is incorporated herein by reference.
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to cellulose nanofibers, a methd for producing the same, a composite resin composition, and a molded body.
  • 2. Background Art
  • Cellulose nanofibers have been used as a reinforcing material for polymeric composite materials in the related art. The cellulose nanofibers are generally obtained by mechanically shearing cellulose fibers such as pulp.
  • For example, Japanese Patent Application, First Publication No. 2000-17592 discloses fibrillar cellulose that is obtained by treating an aqueous cellulose pulp suspension with a high-pressure homogenizer.
  • In addition, Japanese Patent Application, First Publication No. H09-291102 discloses acetyl cellulose ultrafine fibers that are obtained by acetylating ultrafine cellulose fibers produced from bacteria. The ultrafine cellulose fibers produced from bacteria have a mass-average polymerization degree of 1700 or higher. Accordingly, the ultrafine cellulose fibers produced from bacteria are excellent in terms of Young's modulus and tensile strength.
    • SUMMARY OF THE INVENTION
  • The invention employs the following means.
  • (1) The cellulose nanofibers of the present invention have an average polymerization degree of 600 to 30000, an aspect ratio of 20 to 10000, an average diameter of 1 nm to 800 nm, and an Iβ-type crystal peak in an X-ray diffraction pattern. (2) In the cellulose nanofibers of the present invention, hydroxyl groups are preferably chemically modified with a modification group. (3) In the cellulose nanofibers of the present invention, a saturated absorptivity in an organic solvent having an SP value of 8 to 13 is preferably 300% by mass to 5000% by mass. (4) In the cellulose nanofibers of the present invention, the organic solvent is preferably a water-insoluble solvent. (5) In the cellulose nanofibers of the present invention, the hydroxyl groups are preferably esterified or etherified by the modification group. (6) In the cellulose nanofibers of the present invention, 0.01% to 50% of the total hydroxyl groups are preferably chemically modified. (7) The composite resin composition of the present invention contains the cellulose nanofibers in a resin. (8) An average light transmittance at 400 nm to 700 nm of the composite resin composition of the present invention is preferably 60% or more. (9) The molded body of the present invention is obtained by molding the composite resin composition. (10) In the method for producing the cellulose nanofibers of the present invention, a cellulose raw material is defibrated and chemically modified in a solution containing an ionic liquid.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a view illustrating results of X-ray diffraction analysis of the cellulose nanofibers of the present invention.
    •  BEST MODE FOR CARRYING OUT THE INVENTION
  • The average polymerization degree of the cellulose nanofibers of the present invention is 600 to 30000. The average polymerization degree is preferably 600 to 5000, and more preferably 800 to 5000. If the average polymerization degree is 600 or higher, a sufficient reinforcing effect can be obtained.
  • The cellulose nanofibers in the related art are obtained by performing mechanical shearing such as homogenizing treatment on a raw material of cellulose fibers. Consequently, the cellulose nanofibers in the related art have a low polymerization degree, and a sufficient reinforcing effect cannot be obtained. Moreover, since the mechanical shearing seriously damages the raw material of cellulose fibers, the strength and the aspect ratio of the obtained cellulose nanofibers are low. According to the method for producing the cellulose nanofibers of the present invention that is described later, the raw material of cellulose fibers is not damaged. Accordingly, it is possible to easily obtain cellulose nanofibers having a polymerization degree of 600 or higher.
  • In order to obtain a sufficient reinforcing effect, the aspect ratio of the cellulose nanofibers of the present invention is 20 to 10000 and more preferably 20 to 2000. In the present specification and Claims, the “aspect ratio” refers to a ratio (average fiber length/average diameter) between an average fiber length and an average diameter of the cellulose nanofibers. As described above, according to the method for producing the cellulose nanofibers of the present invention, the raw material of cellulose fibers is not damaged. Therefore, it is possible to obtain cellulose nanofibers having a long average fiber length and an aspect ratio of 20 or more. Moreover, cellulose nanofibers having an aspect ratio of 10000 or less have a high moldability.
  • The average diameter of the cellulose nanofibers of the present invention is 1 nm to 800 nm, preferably 1 nm to 300 nm, and more preferably 1 nm to 100 nm. If cellulose nanofibers having an average diameter of 1 nm or more are produced, the production cost can be kept low. If cellulose nanofibers having an average diameter of 800 nm or less are produced, decrease in the aspect ratio can be inhibited. As a result, the cellulose nanofibers of the present invention can obtain a sufficient reinforcing effect with a low cost.
  • The cellulose nanofibers of the present invention have an Iβ-type crystal peak in an X-ray diffraction pattern. A cellulose type I is composite crystals of Iα-type crystals and Iβ-type crystals. Cellulose derived from higher plants such as cotton includes more Iβ-type crystals than Iα-type crystals. Bacterial cellulose includes more Iα-type crystals than Iβ-type crystals. Since the cellulose nanofibers of the present invention obtained using wood and the like, they mainly include the Iβ-type crystals.
  • Accordingly, the cellulose nanofibers of the present invention show a pattern unique to the Iβ-type crystals in an X-ray diffraction pattern as shown in FIG. 1.
  • Since the cellulose nanofibers of the present invention mainly include the Iβ-type crystals, the reinforcing effect thereof is superior to that of bacterial cellulose including lots of Iα-type crystals.
  • The cellulose nanofibers of the present invention may be chemically modified so as to enhance its functionality. In order to use the cellulose nanofibers for a composite material, it is preferable to chemically modify hydroxyl groups on the surface of the cellulose nanofibers with a modification group so as to reduce the number of the hydroxyl groups. In this manner, the number of hydrogen bonds formed between the cellulose nanofibers is reduced, whereby strong adhesion between the cellulose nanofibers can be prevented. Consequently, the cellulose nanofibers are easily dispersed in a polymer material, whereby excellent interfacial bonds can be formed between the cellulose nanofibers and the polymer material. Due to the chemical modification, the cellulose nanofibers of the present invention have thermal resistance. Accordingly, if the chemically modified cellulose nanofibers of the present invention are mixed with other material, it is possible to impart thermal resistance to other material.
  • The proportion of hydroxyl groups chemically modified by a modification group with respect to total hydroxyl groups in the cellulose nanofibers is preferably 0.01% to 50%, and more preferably 10% to 20%.
  • The chemical modification simply needs to cause a reaction with a hydroxyl group. Etherification or esterification of the cellulose nanofibers is preferable since the chemical modification can be performed simply and efficiently.
  • As etherification agents, alkyl halides such as methyl chloride and ethyl chloride; dialkyl carbonate such as dimethyl carbonate and diethyl carbonate; dialkyl sulfate such as dimethyl sulfate and diethyl sulfate; alkylene oxides such as ethylene oxide and propylene oxide; and the like are preferable. In addition, the etherification is not limited to alkyl etherification caused by the above etherification agents, and etherification caused by benzyl bromide, silyl etherification, and the like are also preferable. Examples of silyl etherification agents include alkoxysilanes such as n-butoxytrimethylsilane, tert-butoxytrimethylsilane, sec-butoxytrimethylsilane, isobutoxytrimethylsilane, ethoxytriethylsilane, octyldimethylethoxysilane, and cyclohexyloxytrimethylsilane; alkoxysiloxanes such as butoxypolydimethylsiloxane; and silazanes such as hexamethyldisilazane, tetramethyldisilazane, and diphenyltetramethyldisilazane. In addition, silyl halides such as trimethylsilyl chloride and diphenylbutyl chloride; and silyl trifluoromethane sulfonates such as t-butyldimethylsilyl trifluoromethane sulfonate can also be used.
  • Examples of esterification agents include a carboxylic acid that may have a hetero atom, a carboxylic anhydride, and a carboxylic halide. As the esterification agents, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, and a derivative of these are preferable, and acetic acid, acetic anhydride, and butyric anhydride are more preferable.
  • Among the types of etherification and the esterification, alkyl etherification, alkyl silylation, and alkyl esterification are preferable since dispersibility in a resin is improved by these reactions.
  • The saturated absorptivity of the cellulose nanofibers of the present invention chemically modified described above is preferably 300% by mass to 5000% by mass in an organic solvent having a solubility parameter (hereinbelow, referred to as an SP value) of 8 to 13. The cellulose nanofibers dispersed in the organic solvent having the above SP value have high affinity with a lipophilic resin and have a high reinforcing effect.
  • Examples of organic solvents having an SP value of 8 to 13 include acetic acid, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, methyl propyl ketone, methyl isopropyl ketone, xylene, toluene, benzene, ethyl benzene, dibutyl phthalate, acetone, isopropanol, acetonitrile, dimethyl formamide, ethanol, tetrahydrofuran, methyl ethyl ketone, cyclohexane, carbon tetrachloride, chloroform, methylene chloride, carbon disulfide, pyridine, n-hexanol, cyclohexanol, n-butanol, nitromethane, and the like.
  • As the organic solvent, water-insoluble solvents (solvents that do not mix with water at 25° C. water at any ratio) such as xylene, toluene, benzene, ethylbenzene, dichloromethane, cyclohexane, carbon tetrachloride, methylene chloride, ethyl acetate, carbon disulfide, cyclohexanol, and nitromethane are more preferable. That is, the cellulose nanofibers of the present invention that are chemically modified as described above can be dispersed even in a water-insoluble solvent. Therefore, while cellulose nanofibers in the related art are not easily dispersed in a lipophilic resin, the cellulose nanofibers of the present invention that are chemically modified as described above can be easily dispersed in a lipophilic resin.
  • As the lipophilic resin, resins that dissolve poorly in water and are widely used as an industrial material required to have water resistance are preferable. The lipophilic resin may be either a thermoplastic resin or a thermosetting resin. Examples of the lipophilic resin particularly include a plant-derived resin, a resin formed of carbon dioxide as a raw material, an ABS resin, alkylene resins such as polyethylene and polypropylene, a styrene resin, a vinyl resin, an acrylic resin, an amide resin, an acetal resin, a carbonate resin, a urethane resin, an epoxy resin, an imide resin, a urea resin, a silicone resin, a phenol resin, a melamine resin, an ester resin, an acrylic resin, an amide resin, a fluoro resin, a styrol resin, an engineering plastic, and the like. As the engineering plastic, polyamide, polybutylene terephthalate, polycarbonate, polyacetal, modified polyphenylene oxide, modified polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyether sulfone, polysulfone, polyamide imide, polyether imide, polyimide, polyarylate, polyallyl ether nitrile, and the like are preferable. Among the above resins, two or more kinds of resins may be used as a mixture. In addition, among the above resins, polycarbonate is particularly preferable due to its strong impact strength.
  • As the polycarbonate, generally used polycarbonate can be used. For example, aromatic polycarbonate produced from a reaction between an aromatic dihydroxy compound and a carbonate precursor is preferable.
  • Examples of the aromatic dihydroxy compound include 2,2-bis(4-hydroxyphenyl)propane (“bisphenol A”), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ketone, and the like.
  • Examples of the polycarbonate precursor include carbonyl halides, carbonyl esters, haloformates, and the like. The polycarbonate precursor is specifically phosgene, dihaloformate of, a divalent phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate, and the like.
  • The polycarbonate may be polycarbonates excluding aromatic polycarbonate. Examples of the polycarbonates excluding aromatic polycarbonate include alicyclic polycarbonate, aliphatic polycarbonate, and the like. The polycarbonate resin may be linear or branched. The polycarbonate resin may also be a copolymer of a polymer, which is obtained by polymerizing the aromatic dihydroxy compound and the carbonate precursor, with another polymer.
  • The polycarbonate resin can be produced by a method known in the related art. Examples of methods known in the related art include various methods such as interfacial polymerization, melt transesterification, a pyridine method, and the like.
  • The type of the resin usable in the composite resin composition of the present invention includes a hydrophilic resin, in addition to the lipophilic resin described above. For example, unmodified cellulose nanofibers or cellulose nanofibers chemically modified with hydrophilic functional groups such as a sulfonic acid group, a carboxylic acid group, or a salt of these disperse excellently in a hydrophilic resin and can be suitably used. Examples of the hydrophilic resin include polyvinyl alcohol, resins having undergone hydrophilication treatment, and the like. Among these, polyvinyl alcohol is particularly preferable since this resin is inexpensive and the cellulose nanofibers disperse excellently in this resin.
  • Additives such as a filler, a flame retarding aid, a flame retardant, an antioxidant, a release agent, a colorant, and a dispersant may be further added to the composite resin composition of the present invention.
  • As the filler, carbon fibers, glass fibers, clay, titanium oxide, silica, talc, calcium carbonate, potassium titanate, mica, montmorillonite, barium sulfate, a balloon filler, a beads filler, carbon nanotubes, and the like are usable.
  • As the flame retardant, a halogen-based flame retardant, a nitrogen-based flame retardant, metal hydroxide, phosphorus-based flame retardant, an organic alkali metal salt, an organic alkaline earth metal salt, a silicone-based flame retardant, expandable graphite, and the like are usable.
  • As the flame retarding aid, polyfluoroolefin, antimony oxide, and the like are usable.
  • As the antioxidant, a phosphorus-based antioxidant, a phenol-based antioxidant, and the like are usable.
  • As the release agent, a higher alcohol, carboxylic acid ester, polyolefin wax, polyalkylene glycol, and the like are usable.
  • As the colorant, any colorants such as carbon black and phthalocyanine blue are usable.
  • As the dispersant, for example, surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants and polymeric dispersants are usable, and the surfactant and the polymeric dispersant can be used concurrently, as long as the dispersant enables the cellulose nanofibers to be dispersed in the resin.
  • Since the cellulose nanofibers of the present invention disperse excellently in the resin, the composite resin composition of the present invention that contains the cellulose nanofibers has excellent transparency. For the composite resin composition having a thickness of 20 μm that contains 2% by mass of the cellulose nanofibers, an average light transmittance at 400 nm to 700 nm is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. When the average light transmittance is 60% or more, transparency is maintained, so the composite resin composition can be suitably used for usage requiring transparency.
  • Furthermore, the composite resin composition containing the chemically modified cellulose nanofibers can realize the decrease in a water absorbency and the improvement of thermal resistance without decreasing the light transmittance.
  • At this time, when other additives are contained in the composite resin composition of the present invention, it is preferable to select additives that do not easily lower transparency.
  • The molded body of the present invention is obtained by molding the composite resin composition. Since the molded body of the present invention also contains the cellulose nanofibers, the molded body has excellent strength and thermal resistance. Though not particularly limited, the molded body is used for medical instruments, audio equipment, and the like. Particularly, the molded body is suitably used as a molded body for a camera and a mirror frame that require strength.
  • In the method for producing the cellulose nanofibers of the present invention, a cellulose raw material is defibrated and chemically modified in a solution containing an ionic liquid, whereby the cellulose nanofibers are produced.
  • The cellulose raw material is not particularly limited. Examples of the cellulose raw material include raw materials of natural cellulose such as cotton and hemp; pulp obtained by chemically treating wood, such as kraft pulp and sulfide pulp; semi-chemical pulp; used paper or recycled pulp thereof; and the like. Particularly, the pulp obtained by chemically treating wood is preferable in view of the cost, quality, and influence on the environment.
  • The shape of the cellulose raw material is not particularly limited. However, in view of easiness of treatment and accelerating solvent permeation, the cellulose raw material is preferably used after being appropriately pulverized.
  • The solution (hereinbelow, referred to as a treatment solution) containing the ionic liquid is a solvent that contains an ionic liquid represented by the following chemical formula and an organic solvent.
  • Figure US20120328877A1-20121227-C00001
  • [In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, R2 represents an alkyl group having 1 to 4 carbon atoms or an allyl group, and X− represents halogen, pseudo-halogen, carboxylate having 1 to 4 carbon atoms, or thiocynate.]
  • Examples of the ionic liquid include 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, and 1-propyl-3-methylimidazolium bromide.
  • It is also possible to defibrate the fiber raw material by using only the ionic liquid. However, when even fine fibers are likely to be dissolved due to excessively high solubility, it is preferable to add an organic solvent to the ionic liquid for use.
  • The type of organic solvent to be added may be appropriately selected in consideration of compatibility with the ionic liquid, affinity with cellulose or a chitin material, solubility of a mixed solvent, viscosity, and the like. Particularly, it is preferable to use any one or more organic solvents from among N,N-dimethylacetamide, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, dimethylsulfoxide, acetonitrile, methanol, and ethanol. If these organic solvents are used concurrently, permeation of the ionic liquid into fine cellulose fibers is promoted, whereby destruction of the crystal structure of the fine fibers caused by the ionic liquid can be prevented.
  • The amount of the ionic liquid contained in the treatment solution may be appropriately adjusted since the amount depends on the type of the cellulose raw material, the ionic liquid, and the organic solvent. The amount of the ionic liquid contained in the treatment solution is preferably 20% by mass or more in view of swelling and solubility, and when an organic solvent having high solubility is used, the amount is more preferably 30% by mass or more. When an organic solvent having low solubility such as methanol is used, the amount is particularly preferably 50% by mass or more.
  • The amount of the cellulose raw material added preferably ranges from 0.5% by mass to 30% by mass based on the treatment solution. In view of economic efficiency, the amount of the cellulose raw material added is 0.5% by mass or more, and more preferably 1% by mass or more, based on the treatment solution. On the other hand, in view of uniformity of the defibration degree, the amount of the cellulose raw material added is preferably 30% or less, and more preferably 20%, based on the treatment solution.
  • As a treatment temperature, an appropriate temperature at which the cellulose raw material swells, and a bound substance between fine fibers softens and dissolves may be selected. The treatment temperature is preferably 20° C. to 120° C. in general.
  • If the treatment temperature is 20° C. or higher, the defibration effect is not diminished, in view of the treatment rate and the viscosity of the treatment solution. If the treatment temperature is 120° C. or lower, the bound substance between the fine fibers does not excessively soften and dissolve. Accordingly, when the treatment temperature is 20° C. to 120° C., a yield of the cellulose nanofibers can be maintained.
  • In the method for producing the cellulose nanofibers of the present invention, after the defibration treatment performed in the treatment solution, chemical modification is performed. As the chemical modification, the etherification, esterification, and silylation described above are preferable.
  • According to the method for producing the cellulose nanofibers of the present invention, fibers are not damaged. Accordingly, it is possible to obtain cellulose nanofibers having a polymerization degree of 600 or higher that do not exist in the related art.
    • EXAMPLES
  • Hereinbelow, the present invention will be described in more detail based on examples and comparative examples. But, the present invention is not limited to the following examples.
    • Example 1
  • 2 g of filter paper cut with a pair of scissors to have 3 mm sides was put in a 200 ml flask, and then 50 ml of N,N-dimethylacetamide and 60 g of an ionic liquid 1-butyl-3-methylimidazolium chloride were added to the flask, followed by stirring. Subsequently, the contents in the flask were filtered, thereby obtaining cellulose nanofibers. The obtained cellulose nanofibers were washed and then dispersed in distilled water, and mixed with an aqueous polyvinyl alcohol solution. The resultant was molded into a film, followed by drying. Thereby, a polyvinyl alcohol composite resin composition containing the cellulose nanofibers was obtained. The modification rate of the cellulose nanofibers obtained at this time was 0%.
    • Example 2
  • The cellulose nanofibers obtained in Example 1 were acetylated using acetic anhydride (esterification agent), thereby obtaining acetylated cellulose nanofibers. The modification rate of the cellulose nanofibers obtained at this time was 10%. Thereafter, polycarbonate which had already been dissolved in dichloromethane was mixed with acetylated cellulose nanofibers in the dichloromethane, followed by drying. Thereby, a polycarbonate composite resin composition containing cellulose nanofibers was obtained.
    • Example 3
  • A polycarbonate composite resin composition containing cellulose nanofibers was obtained by the same process as in Example 2, except that the amount of the acetic anhydride was increased by twice that in Example 2. The modification rate of the cellulose nanofibers obtained at this time was 18%.
    • Example 4
  • A polycarbonate composite resin composition containing cellulose nanofibers was obtained by the same process as in Example 2, except that hexamethyldisilazane (silyl etherification agent) was added instead of acetic anhydride. The modification rate of the cellulose nanofibers obtained at this time was 15%.
    • Comparative Example 1
  • A polycarbonate composite resin composition containing cellulose nanofibers was obtained by the same process as in Example 2, except that bacterial cellulose obtained by drying NATA de COCO (manufactured by Fujicco Co., Ltd., average polymerization degree: 3000 or higher, average aspect ratio: 1000 or more, average diameter: 70 nm) was used.
    • Comparative Example 2
  • A polycarbonate composite resin composition containing cellulose nanofibers was obtained in the same process as in Example 2, except that fine crystalline cellulose (manufactured by MERCK LTD., average polymerization degree: 250, average aspect ratio: 10, diameter: crystals having a diameter of 1 μm to 10 μm are mixed) was used.
  • The molded bodies of the respective examples and comparative examples were measured by the following test method, and the results are shown in Table 1.
  • (1) Average Polymerization Degree
  • The average polymerization degree was measured by the copper ethylenediamine method disclosed in “The Society of Polymer Science, Japan, “Polymer material testing method 2”, p. 267, KYORITSU SHUPPAN CO., LTD. (1965)”.
  • (2) Aspect Ratio and Average Diameter
  • The number average fiber diameter and the number average length of the cellulose nanofibers were evaluated by SEM analysis.
  • Specifically, a cellulose nanofiber dispersion was cast on a wafer so as to be observed by SEM, and for each of the obtained images, the values of fiber diameter and length were read out with respect to 20 or more strands of fibers. This operation was performed on at least 3 sheets of images of non-overlapping regions, thereby obtaining information on the diameter and length of a minimum of 30 strands of fiber.
  • From the data of the fiber diameter and length obtained as above, the number average fiber diameter and the number average length could be calculated. From a ratio between the number average length and the number average fiber diameter, the aspect ratio was calculated. When the aspect ratio was 20 to 10000, this was determined to be O, and when the aspect ratio was not 20 to 10000, this was determined to be X.
  • (3) Crystal Structure Analysis (XRD)
  • The crystal structure of the cellulose nanofibers was analyzed using a powder X-ray diffraction instrument Rigaku Ultima IV. When the X-ray diffraction pattern showed the pattern unique to the Iβ-type crystals, this was determined to be O. Cases other than this were determined to be Δ. In addition, when the crystal structure of the cellulose nanofibers was an Iβ-type crystal structure in examples and comparative examples, this was indicated as O, and when the crystal structure was not the Iβ-type crystal structure, this was indicated as X.
  • (4) Modification Rate A1 of Hydroxyl Group
  • The modification rate of hydroxyl groups was calculated from an elemental ratio between carbon, hydrogen, and oxygen that was obtained by elemental analysis.
  • (5) Saturated Absorptivity R
  • First, cellulose nanofibers of a weight (W1) were dispersed in dichloromethane (SP value 9.7), thereby preparing a dispersion of 2 wt %. Subsequently, this dispersion was put in a centrifuge flask, followed by centrifugation for 30 minutes at 4500 G. Thereafter, a transparent solvent layer in the upper portion of the centrifuged dispersion was removed, and then a weight (W2) of a gel layer in the lower portion was measured. From the result, the saturated absorptivity was calculated by the following formula.

  • R=W2/W1×100%
  • For Example 3, the evaluation was performed using two solvents including ethyl acetate (SP value 9.1) and dichloromethane (SP value 9.7). At this time, the amount of ethyl acetate was 1200% by mass, and the amount of dichloromethane was 1500% by mass.
  • When the saturated absorptivity was from 300% by mass to 5000% by mass, this was determined to be O. When the saturated absorptivity was not from 300% by mass to 5000% by mass, this was determined to be A.
  • (6) Saturated Average Light Transmittance
  • A resin film having a thickness of 20 μm and containing 2 wt % of the cellulose nanofibers was prepared, and a transmittance at 600 nm was measured using UV 3600 manufactured by Shimadzu Corporation. When the cellulose nanofibers were not mixed with a resin in visual observation, this was determined to be X.
  • TABLE 1
    Comparative Comparative
    Example 1 Example 2 Example 3 Example 4 Example 1 Example 2
    Polymerization 800 800 800 600 3000 250
    degree
    Aspect ratio 106 100 95 103 1000 10
    Average 100 100 100 100 70 1000
    diameter (nm)
    Crystal type ◯ ◯ ◯ ◯ X ◯
    Modification 0 10 18 15 0 0
    rate (%)
    Saturated Δ ◯ ◯ ◯ Δ Δ
    absorptivity
    XRD ◯ ◯ ◯ ◯ Δ ◯
    Average light 60 80 80 80 X X
    transmittance
    (%)
  • As shown in Table 1, the molded body of the present invention was excellent in terms of the average light transmittance. Moreover, Examples 2 to 4 in which hydroxyl groups of the cellulose nanofibers of the present invention were chemically modified were superior in the saturated absorptivity, compared to Comparative Examples 1 and 2.
  • The molded bodies of the respective examples and comparative examples were measured by the following test method, and the results are shown in Table 2.
  • (1) Moldability
  • The obtained composite resin compositions containing cellulose nanofibers were thermally melted and molded, and the molded state was judged by visual observation. When the moldability was excellent, this was determined to be O, and when the moldability was poor, this was determined to be X.
  • (2) Linear Heat Expansion Coefficient
  • A linear hest expansion coefficient between 100° C. and 180° C. was measured using Thermo plus TMA 8310 manufactured by Rigaku Corporation in an air atmosphere heated at a heating rate of 5° C./min. The size of a test sample was set to 20 mm (length)x5 mm (width). First, a first-run was carried out at a temperature ranging from room temperature to Tg, and then the temperature was cooled to room temperature to carry out a second-run. From the results, a linear heat expansion coefficient was calculated by the following formula.

  • Linear heat expansion coefficient=(length at a point in time of 180° C.−length at a point in time of 40° C.)/length at a point in time of 40° C.×100−100
  • When the linear heat expansion coefficient was 5% or greater, this was determined to be O. When the coefficient was less than 5%, this was determined to be X.
  • TABLE 2
    Comparative Comparative
    Example 1 Example 2 Example 3 Example 4 Example 1 Example 2
    Moldability ◯ ◯ ◯ ◯ X ◯
    Linear heat ◯ ◯ ◯ ◯ ◯ X
    expansion
    coefficient
  • As shown in Table 2, the molded bodies of the present invention obtained in examples showed moldability and linear heat expansion coefficients superior to those of comparative examples.
  • According to the present invention, it is possible to provide cellulose nanofibers having an excellent reinforcing effect, a method for producing the cellulose nanofibers, a composite resin composition containing the cellulose nanofibers, and a molded body obtained by molding the composite resin composition.

Claims (17)

1. Cellulose nanofibers,
wherein an average polymerization degree is 600 to 30000,
an aspect ratio is 20 to 10000,
an average diameter is 1 nm to 800 nm, and
the cellulose nanofibers have an Iβ-type crystal peak in an X-ray diffraction pattern.
2. The cellulose nanofibers according to claim 1,
wherein hydroxyl groups are chemically modified by a modification group.
3. The cellulose nanofibers according to claim 2,
wherein a saturated absorptivity in an organic solvent having an SP value of 8 to 13 is 300% by mass to 5000% by mass.
4. The cellulose nanofibers according to claim 3,
wherein the organic solvent is a water-insoluble solvent.
5. The cellulose nanofibers according to claim 2,
wherein the hydroxyl groups are esterified or etherified by the modification group.
6. The cellulose nanofibers according to claim 2,
wherein 0.01% to 50% of the total hydroxyl groups are chemically modified by the modification group.
7. A composite resin composition comprising the cellulose nanofibers according to claim 1 in a resin.
8. The composite resin composition according to claim 7,
wherein an average light transmittance at 400 nm to 700 nm is 60% or more.
9. A molded body obtained by molding the composite resin composition according to claim 7.
10. A molded body obtained by molding the composite resin composition according to claim 8.
11. A method for producing the cellulose nanofibers according to claim 1,
wherein a cellulose raw material is defibrated and chemically modified in a solution containing an ionic liquid.
12. The cellulose nanofibers according to claim 4,
wherein the hydroxyl groups are esterified or etherified by the modification group.
13. The cellulose nanofibers according to claim 12,
wherein 0.01% to 50% of the total hydroxyl groups are chemically modified by the modification group.
14. A composite resin composition comprising the cellulose nanofibers according to claim 2 in a resin.
15. A molded body obtained by molding the composite resin composition according to claim 14.
16. A composite resin composition comprising the cellulose nanofibers according to claim 4 in a resin.
17. A molded body obtained by molding the composite resin composition according to claim 16.
US13/603,806 2010-03-05 2012-09-05 Cellulose nanofibers, method for producing same, composite resin composition and molded body Abandoned US20120328877A1 (en)

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